Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
  • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
  • C08K5/372—Sulfides, e.g. R-(S)x-R'
  • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
  • C08K5/378—Thiols containing heterocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/20—Thiols; Sulfides; Polysulfides
  • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds

Definitions

• This invention relates to novel thioaminals. It also relates to compositions of organic materials which are stabilized against oxidative degradation by the presence therein of a broader range of thioaminal compounds.
• antioxidants such as compounds with amine and/or sulfide functionality in order to avoid degradation, decomposition, sludge formation, viscosity increases, loss of elasticity, embrittlement and the like.
• US Patent No. 3,535,243 discloses the use of diaminonaphthalenes as antioxidants for ester lubricants.
• US Patent No. 3,536,706 discloses phenothiazines for similar purposes.
• US Patent No. 4,785,095 discloses N-substituted phenothiazines as antioxidants for lubricating oils.
• US Patent 2,281,521 discloses antioxidants which are reaction products of mercaptans, formaldehyde and secondary or tertiary aromatic amines as shown below.
• US Patent No. 4,402,842 relates to a product by process wherein the product is made by reacting an alkyl, alkenyl, cycloalkyl or cycloalkenyl mono- or diamine with certain mercaptans and aldehydes and the use thereof as friction reducing additives.
• US 2,703,784 discloses the use of corrosion inhibitors containing a product made from an aldehyde, a mercaptan and a dimercaptan.
• US 2,786,616 discloses lubricant compositions containing products derived from formaldehyde, aliphatic amines and an alkylthiohydroquinone.
• US 2,971,909 discloses a non-corrosive lubricant composition containing the reaction product of 2-amino-5-thio-1,3,4-dithiazolidine, an aldehyde and a mercaptan.
• US 3,399,041 discloses a method of stabilizing lubricating oils by the addition thereto of a diaminodithiaalkane. The instant thioaminals are not specifically disclosed in any of the above publications.
• the invention pertains to compositions stabilized against degradation which comprise
• T1, T2, T3, A1-A3 and L1-L3 groups are as follows.
• T1 is for example methyl, pentyl, octyl, decyl, octadecyl eicosyl, or pentaeicosyl.
• T1 is C8-C12alkyl, especially octyl, tert-nonyl, or tert.dodecyl, or -CH2CH2OH.
• T1 is C6-C12aryl, it is preferably phenyl.
• R2 is preferably tert.-butyl or tert.-octyl.
• T3 is preferably H, methyl, butyl, hexyl, phenyl, tolyl or xylyl and most preferably H.
• A1 and A3 are preferably phenyl, naphthyl, tolyl or xylyl.
• Another preferred embodiment of A2 is -CH(T3)-S-T1.
• A3 is preferably -CH(T3)-S-T1, C1-C12alkyl or phenyl.
• L1 is preferably C2-C6alkylene and most preferably C6alkylene.
• L2 is preferably phenylene or wherein L3 is CH2.
• T2 is preferably -CH(T3)-S-T1 or H with A2 being phenyl.
• the stabilizing compounds utilized in the compositions of this invention correspond to formulae I to VIII: wherein T1, R x and R y are as defined in formula (H), R1 is C1-C30alkyl, C5-C12-cycloalkyl, phenyl or -CH2CH2OH; T2 is or H when A2 is phenyl; R3 is H, C1-C14alkyl, phenyl or phenyl-C1-C4alkyl; R4 is C1-C16alkyl or two R4 groups together are pentamethylene; A1, A2 and A3, independently of each other, are H, C1-C18alkyl, or -CH(R3)-S-R5 wherein R2 is H, C1-C30alkyl or -C(R6)(R7)phenyl, and R5 is C6-C12aryl, C1-C30alkyl, C5-C12cycloalkyl or -CH2
• R1-R4, A1-A3 and L1-L3 groups are as follows.
• R1 is C1-C30alkyl
• R1 is for example methyl, pentyl, decyl, octadecyl, eicosyl, and pentaeicosyl.
• R1 is C8-C12alkyl, especially octyl, tert.nonyl or tert.dodecyl or -CH2CH2OH.
• R2 is preferably tert.-butyl or tert.-octyl.
• R3 is preferably H, methyl, butyl or hexyl and most preferably H.
• R4 is preferably pentamethylene.
• A1 or A2 are preferably phenyl, naphthyl, tolyl or xylyl.
• Another preferred embodiment of A2 is -CH(R3)-S-R5.
• A3 is preferably -CH(R3)-S-R5, C1-C12alkyl or phenyl.
• L1 is preferably C2-C6alkylene and most preferably C6alkylene.
• L2 is preferably phenylene or wherein L3 is -CH2-.
• the thioaminal compounds can be prepared by a condensation reaction using the requisite amount of the appropriately substituted thiol, aldehyde and amine.
• compounds of formula A and I are prepared from the appropriately substituted monothiol, aldehyde and monoamine.
• Compounds of formula B and II are correspondingly prepared from a dithiol, an aldehyde and a monoamine.
• Compounds of formula C, F, II and VI are prepared form a monothiol, an aldehyde and a diamine.
• the polymeric or oligomeric compounds of formula D and IV are made from a dithiol, an aldehyde and a diamine.
• Compounds of formula G can be synthesized by reacting the hydroxy or alkoxy diphenylamine with formaldehyde and a monothiol in the presence or absence of a solvent, e.g. ethanol, isopropanol or the like.
• a solvent e.g. ethanol, isopropanol or the like.
• compounds of formula F can be obtained by treatment of the corresponding 4-amino or 4-N-alkyl(aryl)amino diphenylamine with the necessary amount of monothiol and aldehyde.
• compounds of formula H can be prepared by reacting together a mixture of 2 moles of a monothiol, 2 moles of formaldehyde and 1 mole of the corresponding bis-amine naphthalene product.
• the compounds utilized in the present invention are particularly effective in stabilizing organic materials subject to oxidative or thermal degradation such as lubricants, elastomers and other polymers.
• Substrates in which these compounds are particularly useful are lubricants and elastomers. These preferred substrates may be defined as:
• polymers which can be stabilized include
• the compounds of the present invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application.
• An advantageous range is from about 0.5 to about 2%, and espacially 0.1 to about 1%.
• the stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
• the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
• the resulting stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following.
• Alkylated monophenols for example,
• phenyl salicylate for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
• ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester for example, ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ -carbomethoxy-cinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, ⁇ -carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methyl-indoline.
• additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of
• N,N′-diphenyloxalic acid diamide N-salicylal-N′-salicyloylhydrazine, N,N′-bis-salicyloylhydrazine, N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamino 1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.
• triphenyl phosphite for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldiakyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, di-isodecylpentaethritol diphosphite, di-(2,4-di-tert-butylphenyl)pentaethritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4′-diphenylylenediphosphonite.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-( ⁇ -dodecylmercapto)-propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
• mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyl-dithiocarbamate
• dioctadecyl disulfide pentaerythritol tetrakis-( ⁇ -dodecylmercapto)-propionat
• N-benzyl-alpha-phenyl nitrone N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived
• melamine for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
• the lubricant composition may also contain other additives, such as rust inhibitors, viscosity regulators, pour point depressants, dispersing agents or detergents, said additives being widely known and used in lubricants.
• Octanethiol (14.6 g., 0. 10 mol), 4,4′-methylenedianiline (9.9 g., 0.05 mol) and 37 % aqueous formaldehyde solution (22.7 g, 0.28 mol) in 150 ml methanol are refluxed for 7 hours during which time an oily mixture is formed. The the mixture is allowed to stand overnight at room temperature. After completing the reaction, the mixture is concentrated by evaporation and the product is isolated.
• a 150 N paraffinic mineral oil (50 grams) containing 0.25 % by weight of a test compound and 5 mL of water is added to a galss container having a copper coil which is housed inside a bomb fitted with a pressure gauge as described in ASTM D 2272.
• the bomb is charged with oxygen to a pressure of 90 psi (620 kPa), placed in a constant temperature oil bath at 150 °C and rotated axially at 100 rpm at a 30° angle from the horizontal.
• the time required for the test sample to react with a given volume of oxygen is measured, completion of reaction being indicated by a specific drop in pressure (25 psi, 172 kPa) from the plateau pressure originally observed. This time is reported as minutes to failure
• the antioxidant effectiveness of the instant stabilizers in engine oils is evaluated by ASTM test method, D4742.
• a 1.5 gram test sample of a 10W-30 engine oil, formulated to meet SD/CC quality level, containing 0.5% by weight of the test compound is placed in the test apparatus.
• the test is then completed according to the standard method procedure and the oxidation induction time, in minutes, is determined (reported in the table below). A longer induction time indicates greater oxidation stability.
• This example illustrates the process stabilizing effectiveness of the instant stabilizers in elastomers.

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• 1991
  • 1991-08-09 EP EP19910810627 patent/EP0473542B1/de not_active Expired - Lifetime
  • 1991-08-09 DE DE1991601956 patent/DE69101956T2/de not_active Expired - Fee Related
  • 1991-08-14 CA CA 2049189 patent/CA2049189A1/en not_active Abandoned
  • 1991-08-15 MX MX9100671A patent/MX9100671A/es unknown
  • 1991-08-15 BR BR919103500A patent/BR9103500A/pt unknown
  • 1991-08-16 JP JP22965891A patent/JPH04316553A/ja active Pending

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